Materials and Physical Measurements
The chemicals and solvents were analytical grade commercial sources and used without further purification. FT-IR spectra were acquired in KBr pellets at a Mattson Alpha-Centauri spectrometer with the scan range of 4000 − 400 cm− 1 and the bands were denoted as strong (s), medium (m) and weak (w) at the preparation section. The respective asymmetrical/symmetrical IR vibration bands of the corresponding groups were expressed as νas/νs. The C/H/N/S were acquired microanalytically by a Perkin-Elmer elemental analyzer with Model 2400II. The melting points were recorded by an XT-4 thermal apparatus without correction.
Preparation of the salts 1–4
a. (triphenylmethylamine) : (p-toluenesulfonic acid) [(Htpma) · (tolsa)] (1)
A solution of p-toluenesulfonic acid (34.4 mg, 2.0 mmol) in methanol (8 ml) was added dropwise to a vigorously stirred solution of triphenylmethylamine (52.1 mg, 2.0 mmol) in methanol (3 ml) over a period of 5 min. The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left standing at room temperature for 6 days, colorless block crystals were isolated after slow evaporation of the methanol solution in air. The crystals were collected and dried in air to give [(Htpma) · (tolsa)] (1). (yield: 58.0 mg, 67.2%). mp 119–121°C. Elemental analysis: Calc. for C26H25NO3S (431.54): C, 72.29; H, 5.79; N, 3.24; S, 7.42. Found: C, 72.18; H, 5.72; N, 3.16; S, 7.33. Infrared spectrum (cm− 1): 3448s(νas(NH)), 3360s(νs(NH)), 3230m, 3139m, 3045m, 2962m, 2870m, 1626m, 1586m, 1540m, 1496m, 1448m, 1404m, 1360m, 1313m, 1270m, 1230m, 1190m, 1148m, 1108m, 1066m, 1022m, 980m, 936m, 888m, 842m, 798m, 754m, 710m, 666m, 618m.
b. (triphenylmethylamine) : (2-naphthalenesulfonic acid) [(Htpma) · (nptolsa)] (2)
A solution of 2-naphthalenesulfonic acid (41.6 mg, 2.0 mmol) in methanol (10 ml) was added dropwise to a vigorously stirred solution of triphenylmethylamine (52.1 mg, 2.0 mmol) in methanol (3 ml) over a period of 5 min. The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left standing at room temperature for 13 days, colorless block crystals were isolated after slow evaporation of the methanol solution in air. The crystals were collected and dried in air to give [(Htpma) · (nptolsa)] (2). (yield: 49.0 mg, 52.4%). mp 135–136°C. Elemental analysis: Calc. for C29H25NO3S (467.56): C, 74.43; H, 5.35; N, 2.99; S, 6.84. Found: C, 74.35; H, 5.28; N, 2.93; S, 6.77. Infrared spectrum (cm− 1): 3430s(νas(NH)), 3357s(νs(NH)), 3245m, 3176m, 3124m, 3058m, 1620m, 1566m, 1522m, 1478m, 1435m, 1393m, 1350m, 1308m, 1263m, 1220m, 1188m, 1144w, 1100m, 1065m, 1024m, 978m, 934m, 888m, 846m, 802m, 758m, 716m, 668m, 620m.
c. (triphenylmethylamine) : (3-nitrophthalic acid) [(Htpma+) · (3-Hnpta−)] (3)
A solution of 3-nitrophthalic acid (42.2 mg, 2.0 mmol) in methanol (12 ml) was added dropwise to a vigorously stirred solution of triphenylmethylamine (52.1 mg, 2.0 mmol) in methanol (3 ml) over a period of 5 min. The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left standing at room temperature for 12 days, colorless block crystals were isolated after slow evaporation of the methanol solution in air. The crystals were collected and dried in air to give [(Htpma+) · (3-Hnpta−)] (3). (yield: 55.0 mg, 58.4%). mp 180–182°C. Elemental analysis: Calc. for C27H22N2O6 (470.47): C, 68.87; H, 4.68; N, 5.95. Found: C, 68.79; H, 4.63; N, 5.88. Infrared spectrum (cm− 1): 3576s(ν(OH)), 3444s(multiple, νas(NH)), 3374s(νs(NH)), 3248m, 3133m, 3075m, 2982m, 1734s(ν(C = O)), 1625m, 1584s(νas(CO2−)), 1530s(νas(NO2)), 1488m, 1446m, 1390s(νs(CO2−)), 1328s(νs(NO2)), 1291s(ν(C-O)), 1246m, 1202m, 1157m, 1115m, 1072m, 1034m, 989m, 945m, 900m, 856m, 812m, 770m, 726m, 684m, 640m, 608m.
d. (triphenylmethylamine) : (5-nitroisophthalic acid) [(Htpma+) · (5-Hnipta−)] (4)
A solution of 5-nitroisophthalic acid (42.2 mg, 2.0 mmol) in methanol (10 ml) was added dropwise to a vigorously stirred solution of triphenylmethylamine (52.1 mg, 2.0 mmol) in methanol (3 ml) over a period of 5 min. The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left standing at room temperature for 9 days, colorless block crystals were isolated after slow evaporation of the methanol solution in air. The crystals were collected and dried in air to give [(Htpma+) · (5-Hnipta−)] (4). (yield: 49.0 mg, 52.08%). mp 200–202°C. Elemental analysis: Calc. for C27H22N2O6 (470.47): C, 68.87; H, 4.68; N, 5.95. Found: C, 68.83; H, 4.64; N, 5.91. Infrared spectrum (cm− 1): 3580s(ν(OH)), 3448s(multiple, νas(NH)), 3356s(νs(NH)), 3274m, 3155m, 3078m, 2989m, 1712s(ν(C = O)), 1600s(νas(CO2−)), 1558m, 1520s(νas(NO2)), 1476m, 1436m, 1388s(νs(CO2−)), 1346m, 1314s(νs(NO2)), 1280s(ν(C-O)), 1240m, 1195m, 1152m, 1106m, 1060m, 1018m, 978m, 932m, 885m, 840m, 794m, 750m, 707m, 665m, 624m.
X-ray Crystallography and Data Collection
SCXRD studies were carried out via a Bruker SMART 1000 CCD diffractometer at 50 kV/40 mA using Mo Kα radiation (λ = 0.71073 Å, monochromator graphite). Data collection and reduction were completed by the SMART and SAINT softwares [14]. The structures were solved by direct methods and the non-Hs were subjected to anisotropic refinement by full-matrix least squares on F2 by the SHELXTL package [15]. All Hs were put in geometrically calculated positions with O-H = 0.82 Å, N-H = 0.89 Å, C-H = 0.93 Å (aryl), or 0.96 Å (CH3) and with Uiso = 1.2Ueq(C,N) and Uiso = 1.5Ueq(O), and included in the refinement in a riding-model approximation. Details of the data collection and structure refinement parameters along with the crystallographic data are listed in Table 1, selected bond lengths, bond angles and H-bond geometries are in Tables 2–3.
Table 1
Summary of X-ray crystallographic data for complexes 1–4.
| 1 | 2 | 3 | 4 |
Formula | C26H25NO3S | C29H25NO3S | C27H22N2O6 | C27H22N2O6 |
Fw | 431.54 | 467.56 | 470.47 | 470.47 |
T, K | 293(2) | 298(2) | 298(2) | 293(2) |
Wavelength, Å | 0.71073 | 0.71073 | 0.71073 | 1.54178 |
Crystal system | Tetragonal | Monoclinic | Monoclinic | Monoclinic |
space group | I-4c2 | Cc | C2/c | P2(1)/c |
a, Å | 19.550(3) | 31.584(3) | 29.762(3) | 9.2859(3) |
b, Å | 19.550(3) | 19.5233(18) | 8.1228(9) | 23.0126(7) |
c, Å | 24.578(7) | 20.4134(19) | 21.950(2) | 10.9364(4) |
α, deg. | 90 | 90 | 90 | 90 |
β, deg. | 90 | 129.393(5) | 117.436(4) | 102.813(3) |
γ, deg. | 90 | 90 | 90 | 90 |
V, Å3 | 9394(3) | 9727.6(15) | 4709.5(8) | 2278.83(13) |
Z | 16 | 16 | 8 | 4 |
Dcalcd, Mg/m3 | 1.221 | 1.277 | 1.327 | 1.371 |
Absorption coefficient, mm− 1 | 0.164 | 0.164 | 0.095 | 0.809 |
F(000) | 3648 | 3936 | 1968 | 984 |
Crystal size, mm3 | 0.43 x 0.40 x 0.38 | 0.40 x 0.19 x 0.10 | 0.46 x 0.45 x 0.38 | 0.33 x 0.24 x 0.19 |
θ range, deg | 2.47–28.38 | 2.00–25.02 | 2.62–25.02 | 3.84–66.04 |
| -26 ≤ h ≤ 23 | -37 ≤ h ≤ 34 | -31 ≤ h ≤ 35 | -11 ≤ h ≤ 10 |
Limiting indices | -26 ≤ k ≤ 26 | -23 ≤ k ≤ 21 | -8 ≤ k ≤ 9 | -27 ≤ k ≤ 27 |
| -23 ≤ l ≤ 32 | -17 ≤ l ≤ 24 | -26 ≤ l ≤ 19 | -12 ≤ l ≤ 7 |
Reflections collected | 29275 | 23077 | 11062 | 8012 |
Reflections independent (Rint) | 5864 (0.1134) | 13920 (0.0586) | 4142 (0.0458) | 3959 (0.0334) |
Goodness-of-fit on F2 | 1.015 | 0.962 | 1.009 | 1.074 |
R indices [I > 2σI] | 0.0569, 0.1376 | 0.1136, 0.2719 | 0.0489, 0.1184 | 0.0451, 0.1179 |
R indices (all data) | 0.1819, 0.2125 | 0.1913, 0.3226 | 0.0889, 0.1374 | 0.0625, 0.1295 |
Largest diff. peak and hole, e.Å−3 | 0.225, -0.256 | 0.311, -0.557 | 0.231, -0.249 | 0.202, -0.179 |
Table 2
Selected bond lengths [Å] and angles [°] for 1–4.
1 | | | |
N(1)-C(1) | 1.508(5) | S(1)-O(3) | 1.431(4) |
S(1)-O(1) | 1.437(4) | S(1)-O(2) | 1.450(4) |
S(1)-C(20) | 1.736(5) | O(3)-S(1)-O(1) | 112.9(2) |
O(3)-S(1)-O(2) | 113.3(2) | O(1)-S(1)-O(2) | 111.5(2) |
O(3)-S(1)-C(20) | 105.5(2) | O(1)-S(1)-C(20) | 106.7(2) |
O(2)-S(1)-C(20) | 106.4(2) | | |
2 | | | |
N(1)-C(1) | 1.515(14) | N(2)-C(20) | 1.513(14) |
N(3)-C(39) | 1.520(11) | N(4)-C(58) | 1.517(12) |
O(1)-S(1) | 1.485(7) | O(2)-S(1) | 1.482(7) |
O(3)-S(1) | 1.484(7) | O(4)-S(2) | 1.473(8) |
O(5)-S(2) | 1.480(7) | O(6)-S(2) | 1.467(7) |
O(7)-S(3) | 1.478(7) | O(8)-S(3) | 1.482(7) |
O(9)-S(3) | 1.463(6) | O(10)-S(4) | 1.498(7) |
O(11)-S(4) | 1.472(7) | O(12)-S(4) | 1.455(8) |
S(1)-C(78) | 1.726(9) | S(2)-C(88) | 1.709(10) |
S(3)-C(98) | 1.760(11) | S(4)-C(108) | 1.724(9) |
O(2)-S(1)-O(3) | 111.5(5) | O(2)-S(1)-O(1) | 113.9(5) |
O(3)-S(1)-O(1) | 112.8(5) | O(2)-S(1)-C(78) | 106.9(5) |
O(3)-S(1)-C(78) | 105.1(5) | O(1)-S(1)-C(78) | 105.9(5) |
O(6)-S(2)-O(4) | 113.0(5) | O(6)-S(2)-O(5) | 111.8(5) |
O(4)-S(2)-O(5) | 112.3(4) | O(6)-S(2)-C(88) | 104.9(5) |
O(4)-S(2)-C(88) | 107.7(5) | O(5)-S(2)-C(88) | 106.5(5) |
O(9)-S(3)-O(7) | 112.9(5) | O(9)-S(3)-O(8) | 112.4(5) |
O(7)-S(3)-O(8) | 113.5(5) | O(9)-S(3)-C(98) | 105.2(5) |
O(7)-S(3)-C(98) | 106.4(5) | O(8)-S(3)-C(98) | 105.6(5) |
O(12)-S(4)-O(11) | 112.9(5) | O(12)-S(4)-O(10) | 113.3(5) |
O(11)-S(4)-O(10) | 112.4(5) | O(12)-S(4)-C(108) | 105.6(5) |
O(11)-S(4)-C(108) | 106.7(5) | O(10)-S(4)-C(108) | 105.2(5) |
3 | | | |
N(1)-C(1) | 1.526(2) | N(2)-O(5) | 1.210(3) |
N(2)-O(6) | 1.219(3) | N(2)-C(24) | 1.466(3) |
O(1)-C(20) | 1.210(3) | O(2)-C(20) | 1.299(3) |
O(3)-C(21) | 1.228(3) | O(4)-C(21) | 1.275(3) |
O(1)-C(20)-O(2) | 125.2(2) | O(3)-C(21)-O(4) | 126.7(2) |
4 | | | |
N(1)-C(1) | 1.527(3) | N(2)-O(5) | 1.215(3) |
N(2)-O(6) | 1.216(3) | N(2)-C(26) | 1.475(3) |
O(1)-C(20) | 1.244(2) | O(2)-C(20) | 1.264(2) |
O(3)-C(21) | 1.209(3) | O(4)-C(21) | 1.311(3) |
O(1)-C(20)-O(2) | 124.82(19) | O(3)-C(21)-O(4) | 123.5(2) |
Table 3
Selected bond lengths [Å] and angles [°] for 1–4.
1 | | | |
N(1)-C(1) | 1.508(5) | S(1)-O(3) | 1.431(4) |
S(1)-O(1) | 1.437(4) | S(1)-O(2) | 1.450(4) |
S(1)-C(20) | 1.736(5) | O(3)-S(1)-O(1) | 112.9(2) |
O(3)-S(1)-O(2) | 113.3(2) | O(1)-S(1)-O(2) | 111.5(2) |
O(3)-S(1)-C(20) | 105.5(2) | O(1)-S(1)-C(20) | 106.7(2) |
O(2)-S(1)-C(20) | 106.4(2) | | |
2 | | | |
N(1)-C(1) | 1.515(14) | N(2)-C(20) | 1.513(14) |
N(3)-C(39) | 1.520(11) | N(4)-C(58) | 1.517(12) |
O(1)-S(1) | 1.485(7) | O(2)-S(1) | 1.482(7) |
O(3)-S(1) | 1.484(7) | O(4)-S(2) | 1.473(8) |
O(5)-S(2) | 1.480(7) | O(6)-S(2) | 1.467(7) |
O(7)-S(3) | 1.478(7) | O(8)-S(3) | 1.482(7) |
O(9)-S(3) | 1.463(6) | O(10)-S(4) | 1.498(7) |
O(11)-S(4) | 1.472(7) | O(12)-S(4) | 1.455(8) |
S(1)-C(78) | 1.726(9) | S(2)-C(88) | 1.709(10) |
S(3)-C(98) | 1.760(11) | S(4)-C(108) | 1.724(9) |
O(2)-S(1)-O(3) | 111.5(5) | O(2)-S(1)-O(1) | 113.9(5) |
O(3)-S(1)-O(1) | 112.8(5) | O(2)-S(1)-C(78) | 106.9(5) |
O(3)-S(1)-C(78) | 105.1(5) | O(1)-S(1)-C(78) | 105.9(5) |
O(6)-S(2)-O(4) | 113.0(5) | O(6)-S(2)-O(5) | 111.8(5) |
O(4)-S(2)-O(5) | 112.3(4) | O(6)-S(2)-C(88) | 104.9(5) |
O(4)-S(2)-C(88) | 107.7(5) | O(5)-S(2)-C(88) | 106.5(5) |
O(9)-S(3)-O(7) | 112.9(5) | O(9)-S(3)-O(8) | 112.4(5) |
O(7)-S(3)-O(8) | 113.5(5) | O(9)-S(3)-C(98) | 105.2(5) |
O(7)-S(3)-C(98) | 106.4(5) | O(8)-S(3)-C(98) | 105.6(5) |
O(12)-S(4)-O(11) | 112.9(5) | O(12)-S(4)-O(10) | 113.3(5) |
O(11)-S(4)-O(10) | 112.4(5) | O(12)-S(4)-C(108) | 105.6(5) |
O(11)-S(4)-C(108) | 106.7(5) | O(10)-S(4)-C(108) | 105.2(5) |
3 | | | |
N(1)-C(1) | 1.526(2) | N(2)-O(5) | 1.210(3) |
N(2)-O(6) | 1.219(3) | N(2)-C(24) | 1.466(3) |
O(1)-C(20) | 1.210(3) | O(2)-C(20) | 1.299(3) |
O(3)-C(21) | 1.228(3) | O(4)-C(21) | 1.275(3) |
O(1)-C(20)-O(2) | 125.2(2) | O(3)-C(21)-O(4) | 126.7(2) |
4 | | | |
N(1)-C(1) | 1.527(3) | N(2)-O(5) | 1.215(3) |
N(2)-O(6) | 1.216(3) | N(2)-C(26) | 1.475(3) |
O(1)-C(20) | 1.244(2) | O(2)-C(20) | 1.264(2) |
O(3)-C(21) | 1.209(3) | O(4)-C(21) | 1.311(3) |
O(1)-C(20)-O(2) | 124.82(19) | O(3)-C(21)-O(4) | 123.5(2) |
Table 1. should be inserted here.